Copolymers prepared from polymers of ethylenically polymerizable cyclic ortho esters

ABSTRACT

Ethylenically unsaturated cyclic ortho esters are prepared by the reaction of a hydroxy-substituted cyclic ortho ester such as 4-hydroxymethyl-2-methoxy-2-methyl-1,3-dioxolane with acryloyl chloride, methacryolyl choride, vinylbenzyl chloride or the like. They form polymers, especially EPDM graft copolymers, which are useful in the formation of copolymer-containing compositions with polyesters, polyamides and the like. The copolymer-containing compositions have excellent physical properties and may be employed to compatabilize blends of the same polymers.

This invention relates to new copolymer-containing compositions preparedfrom polymers of ethylenically unsaturated monomers, and moreparticularly from polymers containing cyclic ortho ester functionality.

In recent years, there has been considerable interest in developingpolymer compositions which include normally incompatible polymers.Examples are compositions comprising linear polyesters such aspoly(ethylene terephthalate) and poly(butylene terephthalate) incombination with olefin and olefin-diene polymers.

It might be expected that various properties of the linear polyesters,such as tensile strength, tensile elongation and impact strength, wouldbe improved by the addition of olefin or olefin-diene polymers. However,the resulting blends exhibit incompatability as evidenced by gross phaseseparation and frequently degradation, rather than improvement, ofphysical properties.

One method of compatabilizing otherwise incompatible polymer blends isto incorporate therein a copolymer, typically a block copolymer, of theotherwise incompatible polymers. Copolymers of this type can be formedby incorporating in one polymer structural units which are chemicallyreactive with the other polymer. Thus, for example, linear polyesters orpolyamides having terminal carboxylic acid groups can undergo reactionwith olefin or olefin-diene copolymers containing epoxy groups, eitheras substituents on the polymer chain or as grafted units. Reference ismade, for example, to U.S. Pat. No. 4,965,111. Similarly,amine-terminated polyamides can undergo reaction with olefin orolefin-diene polymers containing integral or grafted maleic anhydridemoieties. The resulting block copolymers do not exhibit the indicia ofincompatibility which are found in simple blends. Moreover, they areoften useful as compatibilizers for blends of the otherwise incompatibleforms of the two polymers.

While polymers containing reactive substituents or grafted units such asepoxy and anhydride groups are known, many of them have not met withwide commercial acceptance. One possible reason is the relative chemicalinactivity of such polymers, whereupon it is difficult to promote thecopolymer-forming reaction to any substantial extent.

The present invention provides a wide variety of copolymer-containingcompositions with excellent properties. Said compositions are preparedfrom polymers, particularly copolymers, of ethylenically unsaturatedmonomers containing highly reactive cyclic ortho ester groups assubstituents.

Accordingly, the invention includes copolymer-containing compositionsprepared by the reaction of at least one polymer capable of nucleophilicsubstitution with at least one polymer containing cyclic ortho estermoieties and comprising structural units of the formula ##STR1##wherein:

R¹ is C₁₋₁₀ primary or secondary alkyl or aralkyl or a C₆₋₁₀ aromaticradical or is an alkylene radical forming a second 5- or 6-membered ringwith C*, and R² is C₁₋₁₀ primary or secondary alkyl or aralkyl or aC₆₋₁₀ aromatic radical, or R¹ and R² together with the atoms connectingthem form a 5-, 6- or 7-membered ring;

R³ is hydrogen or C₁₋₄ primary or secondary alkyl;

R⁴ is an unsubstituted or substituted C₁₋₆ alkylene or C₆₋₁₀ aryleneradical;

R⁵ is hydrogen or methyl;

R⁶ is hydrogen, C₁₋₆ alkyl or a C₆₋₁₀ aromatic radical;

X is a substantially inert linking group;

m is 0 or 1;

n is from 1 to 2-m;

p is 0 or 1; and

x is 0 when R¹ and C* form a ring and is otherwise 1.

In the polymers containing cyclic ortho ester moieties (hereinaftersometimes "ortho ester polymers") used in the preparation of thecompositions of this invention, the R¹ value may be a C₁₋₄ primary orsecondary alkyl radical such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl or secondary butyl, or an aralkyl or aromatic radicalas defined above. Any substituents should be non-reactive under theconditions of the invention; examples are halo, nitro and alkoxy.Unsubstituted primary radicals and especially the methyl radical aregenerally preferred.

It is also possible for R¹ to form a second 5- or 6-membered ring withother portions of the molecule. For this purpose, one of the carbonatoms in the ortho ester ring is designated C* to indicate its role aspart of said second ring.

The R² value may be a C₁₋₄ primary or secondary alkyl, aralkyl oraromatic radical as defined above for R¹. It is also possible for R¹ andR² together to form a 5-, 6- or 7-membered ring with the atomsconnecting them. Thus, the invention includes compositions prepared fromcertain spiro ortho ester compounds.

The R³ radical may be hydrogen or an alkyl radical similar to R¹ and R².It is preferably hydrogen.

The R⁴ radical is an unsubstituted or substituted C₁₋₆ alkylene radical,any substituents being inert to ortho ester formation and reaction witharyl chlorides; e.g., alkoxy. Preferably, R⁴ is methylene.

The R⁶ radical may be hydrogen, alkyl or aryl as previously defined. Itis preferably hydrogen.

The X value may be any linking group which is substantially inert underthe conditions of formation and polymerization of the cyclic orthoesters of the invention and copolymer formation from polymers thereof.Those skilled in the art will understand that a wide variety of groupsfit this description, and the invention is not limited in that respect.

Suitable X groups include unsubstituted and substituted divalentaliphatic, alicyclic and aromatic radicals and combinations thereof, anysubstituents being of the type previously described. Said radicals maybe attached to other divalent radicals such as carbonyl, sulfone,carbamoyl, disubstituted silicon and alkyl- and arylphosphoryl. Thepreferred X groups have the formulas ##STR2##

The ortho ester polymers include those of the type which may be preparedfrom acrylic and methacrylic acid esters, wherein X has formula II, aswell as vinylbenzyl ethers, wherein X has formula III. Bothvinyl-derived (R⁵ is hydrogen) and isopropenyl-derived (R⁵ is methyl)polymers are included; for example, polymers of acrylic and methacrylicacid esters. For the most part, R⁵ is preferably hydrogen when X hasformula III.

The values of m and n depend on whether the cyclic ortho ester moiety isa 5-membered or 6-membered ring. In general, 5-membered rings arepreferred; that is, m is 0 and n is 1. However, the invention alsoincludes polymers in which a 6-membered ring is present, which requireseither than m and n both be 1 or that m be 0 and n be 2.

Also included are polymers in which p is 0; that is, compounds notcontaining an R⁴ value. Most often, p will be 0 when the ortho esterring is a 6-membered ring.

Many of the ethylenically unsaturated cyclic ortho esters which may beconverted to the ortho ester polymers are disclosed and claimed incopending commonly owned application Ser. No. 07/645,179. Esters of thistype may be prepared by the reaction of a hydroxy-substituted orthoester of the formula ##STR3## wherein R¹⁻⁴, m, n and p are as previouslydefined, with a suitable reagent such as acryloyl chloride, methacryloylchloride or a vinylbenzyl chloride. Said reaction takes place underconventional conditions. In the case of acryloyl chloride ormethacryloyl chloride, it typically occurs in the presence of a tertiaryamine as acid acceptor and in solution in a relatively non-polar organicsolvent. The hydroxy-substituted ortho ester and acryloyl ormethyacryloyl chloride may be employed in approximately equimolaramounts, or the chloride may be employed in slight excess. The amine isgenerally present in excess, to ensure neutralization of all the acidicby-product formed.

Reaction between the hydroxy-substituted ortho ester and vinylbenzylchloride is also conducted under conventional conditions, typically inthe presence of an alkaline reagent such as sodium hydroxide. Again, thehydroxy-substituted ortho ester and vinylbenzyl chloride may be employedin roughly equimolar amounts, or, in this case, an excess of the orthoester may be employed. The molar proportion of base is generally aboutequal to that of ortho ester. No solvent is generally necessary,although one may be employed if desired.

The preparation of ethylenically unsaturated ortho esters is illustratedby the following examples. Molecular structures of all products inExamples 1-4 were confirmed by proton and carbon-13 nuclear magneticresonance spectroscopy.

EXAMPLE 1

A 5-liter 3-necked flask fitted with a mechanical stirrer, pressureequalizing addition funnel and nitrogen inlet was charged with 301 grams(2.03 moles) of 4-hydroxymethyl-2-methoxy-2-methyl-l,3-dioxolane, 514grams (5.08 moles) of triethylamine and 2 liters of methylene chloride.The flask was immersed in an ice-water bath and 193.1 grams (2.13 moles)of acryloyl chloride was added over 50 minutes under nitrogen, withstirring. The mixture was stirred at room temperature overnight and thefiltrate was washed twice with 2-liter portions of water, dried overmagnesium sulfate, filtered and vacuum stripped. A free radicalinhibitor, 3-t-butyl-4-hydroxy-5-methylphenyl sulfide, was added in theamount of 200 ppm. to the residue which was then distilled under vacuum.The desired 4-acryloyloxymethyl-2-methoxy-2-methyl-l,3-dioxolanedistilled at 80°-85° C./0.5-1.0 torr.

EXAMPLE 2

The procedure of Example 1 was repeated, employing 281 grams (1.9 moles)of 4-hydroxymethyl-2-methoxy-2-methyl-1,3-dioxolane, 481 grams (4.76moles) of triethylamine and 199 grams (1.9 moles) of methacryloylchloride. The product,4-methacryloyloxymethyl-2-methoxy-2-methyl-l,3-dioxolane, was collectedat 80° C./0.4 torr.

EXAMPLE 3

The procedure of Example 1 was repeated, employing 21 grams (100 mmol.)of 4-hydroxymethyl-2-methoxy-2-phenyl-1,3-dioxolane, 25.3 grams (250mmol.) of triethylamine, 9.5 grams (105 mmol.) of acryloyl chloride and150 ml. of methylene chloride. The crude product was purified by columnchromatography over basic alumina, using 15% (by volume) ethyl acetatein hexane as an eluant, to yield the desired4-acryloyloxymethyl-2-methoxy-2-phenyl-l,3-dioxolane.

EXAMPLE 4

A 4-necked 250-ml. round-bottomed flask equipped with a mechanicalstirrer, a pressure equalizing addition funnel, a condenser and athermometer was charged with 51.9 grams (350 ml.) of4-hydroxymethyl-2-methoxy-2-methyl-1,3 -dioxolane and 14.01 grams (350mmol.) of powdered sodium hydroxide. The slurry was stirred for 15minutes under nitrogen, after which 41.1 grams (270 mmol.) ofvinylbenzyl chloride (isomeric mixture) was added dropwise over 10minutes. The mixture was heated to 80° C., whereupon an exothermicreaction took place which caused the temperature to rise to 140° C. Themixture was stirred overnight under nitrogen, diluted with 400 ml. ofmethylene chloride and 5 ml. of triethylamine and washed twice with 250ml. of aqueous sodium chloride solution. The organic layer was driedover magnesium sulfate, filtered and vacuum stripped, and the residuewas purified by column chromatography over basic alumina using a 2:1 (byvolume) mixture of hexane and methylene chloride as eluant. There wasobtained the desired isomeric mixture of4-(2-methoxy-2-methyl-1,3-dioxolanyl)methyl vinylbenzyl ethers.

The ortho ester polymers may be prepared by polymerization of theethylenically unsaturated cyclic ortho esters under free radicalconditions, either alone or in the presence of other monomers. The term"polymer", as used herein, includes addition homopolymers and,especially, copolymers with one or more other monomers. Such polymersare disclosed and claimed in copending, commonly owned application Ser.No. 07/716,157.

Polymerization by the free radical method may be effected in bulk,solution, suspension or emulsion, by contacting the monomer or monomerswith a polymerization initiator either in the absence or presence of adiluent at a temperature of about 0°-200° C. Suitable initiators includebenzoyl peroxide, hydrogen peroxide, azobisisobutyronitrile,persulfate-bisulfite, persulfate-sodium formaldehyde sulfoxylate,chlorate-sulfite and the like. Alternatively, polymerization may beeffected by irradiation techniques, as by ultraviolet, electron beam orplasma irradiation.

A large variety of polymerizable compounds can be used to form orthoester copolymers. They include the following:

(1) Unsaturated alcohols and esters thereof: Allyl, methallyl, crotyl,1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methylvinyl, 1-phenallyland butenyl alcohols and esters of such alcohols with saturated acidssuch as acetic, phenylacetic, propionic, butyric, valeric, caproic andstearic; with unsaturated acids such as acrylic, α-substituted acrylic(including alkylacrylic, e.g., methacrylic, ethylacrylic, propylacrylic,etc. and arylacrylic such as phenylacrylic), crotonic, oleic, linolenicand linolenic; with polybasic acids such as oxalic, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic and sebacic; withunsaturated polybasic acids such as maleic, fumaric, citraconic,mesaconic, itaconic, methylenemalonic, acetylenedicarobxylic andaconitic; and with aromatic acids, e.g., benzoic, phthalic, terephthalicand benzoylphthalic acids.

(2) Unsaturated acids (examples of which appear above) and estersthereof with lower saturated alcohols, such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl andcyclohexyl alcohols and with saturated lower polyhydric alcohols such asethylene glycol, propylene glycol, tetramethylene glycol, neopentylglycol and trimethylopropane.

(3) Unsaturated lower polyhydric alcohols, e.g., butenediol, and estersthereof with saturated and unsaturated aliphatic and aromatic, monobasicand polybasic acids, examples of which appear above.

(4) Esters of the above-described unsaturated acids, especially acrylicand methacrylic acids, with higher molecular weight monohydroxy andpolyhydroxy materials such as decyl alcohol, isodecyl alochol, oleylalcohol, stearyl alcohol, epoxy resins and polybutadiene-derivedpolyols.

(5) Vinyl cyclic compounds including styrene, o-, m-, p-chlorostyrenes,bromostyrenes, fluorostyrenes, methylstyrenes, ethylstyrenes andcyanostyrenes; di-, tri- and tetrachlorostyrenes, bromostyrenes,fluorostyrenes, methylstyrenes, ethylstyrenes, cyanostyrenes;vinylnaphthalene, vinylcyclohexane, divinylbenzene, trivinylbenzene,allylbenzene and heterocycles such as vinylfuran, vinylpridine,vinylbenzofuran, N-vinyl carbazole, N-vinylpyrrolidone andN-vinyloxazolidone.

(6) Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether,cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether, ethylmethallyl ether and allyl ethyl ether.

(7) Unsaturated ketones, e.g., methyl vinyl ketone and ethyl vinylketone.

(8) Unsaturated amides, such as acrylamide, methacrylamide,N-phenylacrylamide, N-allylacrylamide, N-methylolacrylamide,N-allylcaprolactam and diacetone acrylamide.

(9) Unsaturated aliphatic hydrocarbons, for instance, ethylene,propylene, butenes, butadiene, isoprene, 2-chlorobutadiene and α-olefinsin general.

(10) Unsaturated alkyl halides, e.g., vinyl fluoride, vinyl chloride,vinyl bromide, vinylidene chloride, vinylidene bromide, allyl chlorideand allyl bromide.

(11) Unsaturated acid anhydrides, e.g., maleic, citraconic, itaconic,bis-4-cyclohexane-1,2-dicarboxylic andbicyclo(2.2.1.)-5-heptene-2,3-dicarboxylic anhydrides.

(12) Unsaturated nitriles, e.g., acrylonitrile, methacrylonitrile andother substituted acrylonitriles.

While the use of random addition polymers is within the scope of theinvention, the preferred ortho ester polymers are graft copolymersprepared by grafting the ethylenically unsaturated ortho esters onpreviously formed polymers. More preferably, said previously formedpolymers are copolymers comprising ethylene and propylene structuralunits; and still more preferably, copolymers also comprising structuralunits derived from at least one non-conjugated diene, said copolymersfrequently being identified hereinafter as "EPDM copolymers". Such graftcopolymers may be conveniently prepared by absorption of theethylenically unsaturated ortho ester and a free radical polymerizationcatalyst on the EPDM copolymer followed by grafting, frequently effectedby extrusion at temperatures in the range of about 150°-300° C.

The preparation of ortho ester graft copolymers is illustrated by thefollowing examples.

EXAMPLES 5-9

Mixtures of ethylenically unsaturated ortho esters and 1 gram of2,5-dimethyl-2,5-di(t-butylperoxy)hexane were premixed and combined with1 kilogram of a commercially available EPDM copolymer containing about83 mole percent ethylene and about 5.4 mole percent norbornene units.The blends were stored for about 16 hours at 20° C. to enable the orthoester and polymerization initiator to be completely absorbed by the EPDMpellets, and were then extruded on a twin-screw extruder with zone settemperatures ranging from 120° to 205° C. The extrudates were cooled ina water bath, pelletized and dried in vacuum.

The proportion of the ethylenically unsaturated ortho ester grafted onthe EPDM copolymer was determined by dissolving a sample of the graftcopolymer in xylene at about 130° C., pouring the resulting solutioninto acetone and filtering and drying the purified copolymer, which wasthen analyzed by Fourier transform infrared spectroscopy. Gel contentwas determined by continuous extraction with hot xylene for 48 hoursfollowed by drying and weighing of the insoluble residue. The resultsare given in Table I, with all percentages being by weight.

                                      TABLE I                                     __________________________________________________________________________                      Example                                                     Ortho ester:      5    6    7    8    9                                       __________________________________________________________________________    Example           1      1    1  2    3                                       Percent based on EPDM copolymer                                                                   0.3                                                                                 1.0                                                                                3.0                                                                               1.0                                                                              1.3                                     Amount grafted, % >90  >90  >90  50   --                                      Gel, %            0     40   40  0    --                                      __________________________________________________________________________

The ortho ester polymers react with other polymers containing reactivegroups, particularly those capable of nucleophilic substitution such asamine, hydroxy, thio and carboxy groups and functional derivativesthereof, to form the copolymer-containing compositions of the presentinvention. Included are copolymer-containing compositions with polymersotherwise incompatible with EPDM copolymers, including linear polyestersand polyamides.

By reason of the presence of the copolymer, the compositions of thisinvention are compatible and may be molded into articles havingexcellent physical properties. They are also useful for furthercompatibilizing blends of the two polymers to form molding compositionshaving similar excellent properties.

Polyesters suitable for preparing the compositions of this inventioninclude those comprising structural units of the formula ##STR4##wherein each R⁶ is independently a divalent aliphatic, alicyclic oraromatic hydrocarbon or polyoxyalkylene radical and A¹ is a divalentaromatic radical. Such polyesters include thermoplastic polyestersillustrated by poly(alkylene dicarboxylates), elastomeric polyesters,polyarylates, and polyester copolymers such as copolyestercarbonates.Because the principal reaction which occurs with the ortho ester groupsinvolves a carboxylic acid group of the polyester, it is highlypreferred that said polyester have a relatively high carboxylic endgroup concentration. Concentrations in the range of about 5-250microequivalents per gram are generally suitable, with 20-150microequivalents per gram being preferable and 20-80 being particularlydesirable.

The polyester may include structural units of the formula ##STR5##wherein R⁶ is as previously defined, R⁷ is a polyoxyalkylene and A² is atrivalent aromatic radical. The A¹ radical in formula V is most often p-or m-phenylene or a mixture thereof, and A² in formula VI is usuallyderived from trimellitic acid and has the structure ##STR6##

The R⁶ radical may be, for example, a C₂₋₁₀ alkylene radical, a C₆₋₁₀alicyclic radical, a C₆₋₂₀ aromatic radical or a polyoxyalkylene radicalin which the alkylene groups contain about 2-6 and most often 4 carbonatoms. As previously noted, this class of polyesters includes thepoly(alkylene terephthalates) and the polyarylates. Poly(alkyleneterephthalates) are frequently preferred, with poly(ethyleneterephthalate) and poly(butylene terephthalate) being most preferred.

The preferred polyesters are poly(ethylene terephthalate) andpoly(butylene terephthalate), generally having a number averagemolecular weight in the range of about 20,000-70,000, as determined byintrinsic viscosity (IV) at 30° C. in a mixture of 60% (by weight)phenol and 40% 1,1,2,2-tetrachloroethane.

Polyamides may also be employed for the formation of the compositions ofthe invention. Included are those prepared by the polymerization of amonoamino-monocarboxylic acid or a lactam thereof having at least 2carbon atoms between the amino and carboxylic acid group, ofsubstantially equimolar proportions of a diamine which contains at least2 carbon atoms between the amino groups and a dicarboxylic acid, or of amonoaminocarboxylic acid or a lactam thereof as defined above togetherwith substantially equimolar proportions of a diamine and a dicarboxylicacid. (The term "substantially equimolar" proportions includes bothstrictly equimolar proportions and slight departures therefrom which areinvolved in conventional techniques for stabilizing the viscosity of theresultant polyamides.) The dicarboxylic acid may be used in the form ofa functional derivative thereof, for example, an ester or acid chloride.

Examples of the aforementioned monoamino-monocarboxylic acids or lactamsthereof which are useful in preparing the polyamides include thosecompounds containing from 2 to 16 carbon atoms between the amino andcarboxylic acid groups, said carbon atoms forming a ring containing the--CO--NH-- group in the case of a lactam. As particular examples ofaminocarboxylic acids and lactams there may be mentioned ε-aminocaproicacid, butyrolactam, pivalolactam, ε-caprolactam, capryllactam,enantholactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoicacids.

Diamines suitable for use in the preparation of the polyamides includethe straight chain and branched chain alkyl, aryl and alkaryl diamines.Illustrative diamines are trimethylenediamine, tetramethylenediamine,pentamethylenediamine, octamethylenediamine, hexamethylenediamine (whichis often preferred), trimethylhexamethylenediamine, m-phenylenediamineand m-xylylenediamine.

The dicarboxylic acids may be represented by the formula

    HOOC--Y--COOH

wherein Y is a divalent aliphatic or aromatic group containing at least2 carbon atoms. Examples of aliphatic acids are sebacic acid,octadecanedioic acid, suberic acid, glutaric acid, pimelic acid andadipic acid.

Both crystalline and amorphous polyamides may be employed, with thecrystalline species often being preferred by reason of their solventresistance. Typical examples of the polyamides or nylons, as these areoften called, include, for example, polyamide-6 (polycaprolactam), 66(polyhexamethylene adipamide), 11, 12, 63, 64, 6/10 and 6/12 as well aspolyamides from terephthalic acid and/or isophthalic acid andtrimethylhexamethylenediamine; from adipic acid and m-xylylenediamines;from adipic acid, azelaic acid and 2,2-bis(p-aminophenyl)propane or2,2-bis-(p-aminocyclohexyl)propane and from terephthalic acid and4,4'-diaminodicyclohexylmethane. Mixtures and/or copolymers of two ormore of the foregoing polyamides or prepolymers thereof, respectively,are also within the scope of the present invention. Preferred polyamidesare polyamide-6, 46, 66, 11 and 12, most preferably polyamide-66.

For the preparation of the compositions of this invention, a blendingmethod which results in the formation of an intimate blend is preferred.Suitable procedures include solution blending, although such proceduresare of limited applicability to many polyesters and polyamides by reasonof their insolubility in most common solvents. For this reason andbecause of the availability of melt blending equipment in commercialpolymer processing facilities, melt reaction procedures are generallypreferred. Conventional melt blending procedures and equipment may beemployed, with extrusion often preferred because of its relativeconvenience and particular suitability. Typical reaction temperaturesare in the range of about 175°-350° C.

Those skilled in the art will be familiar with blending methods andapparatus capable of intimately blending resinous constituents,especially by kneading. They are exemplified by disc-pack processors andvarious types of extrusion equipment. Illustrations of the latter arecontinuous mixers; single screw kneading extruders; counterrotating,non-intermeshing twin screw extruders having screws which includeforward-flighted compounders, cylindrical bushings and/or left-handedscrew elements; corotating, intermeshing twin screw extruders; andextruders having screws which include at least one and preferably atleast two sections of kneading block elements.

In addition to copolymer, the compositions of this invention may alsocontain unreacted polyester, polyamide or the like. In any event, moldedparts produced from said compositions are generally ductile and havehigher impact strengths, tensile strengths and/or tensile elongationsthan those produced from simple blends, which are incompatible and oftenexhibit brittleness or delamination.

There may also be present in the compositions of this inventionconventional ingredients such as fillers, flame retardants, pigments,dyes, stabilizers, anti-static agents, crystallization aids, moldrelease agents and the like, as well as resinous components notpreviously discussed including auxiliary impact modifying polymers.

The proportions of ortho ester polymer, other polymer and other resinousmaterials are not critical; they may be widely varied to providecompositions having the desired properties. Most often, the ortho esterpolymer is employed in an amount in the range of about 5-95%, preferablyabout 5-65%, of the composition by weight.

The preparation of the compositions of this invention is illustrated bythe following examples. All percentages are by weight.

EXAMPLES 10-17

Dry blends comprising ortho ester-grafted EPDM copolymers andpoly(butylene terephthalate) were prepared and extruded at temperaturesin the range of 250° C. The extrudates were the desiredcopolymer-containing compositions; they were pelletized, dried andmolded into test specimens which were tested for tensile strength andelongation (ASTM procedure D638) and notched Izod impact strength (ASTMprocedure D256).

The results are given in Tables II and III, in comparison with fivecontrols employing (A-D) a blend prepared from unfunctionalized EPDMcopolymer, and (E) a blend prepared from EPDM copolymer similarlygrafted with 3% glycidyl methacrylate.

                  TABLE II                                                        ______________________________________                                                                  Con-   Con-                                                     Example       trol   trol                                                     10    11      12      A    E                                      ______________________________________                                        Polyester, parts                                                                            50      50      50    50   50                                   Ortho ester-grafted                                                           EPDM:                                                                         Example       5       6       8     --   --                                   Parts         50      50      50    50   50                                   Tensile strength, MPa.                                                                      16.9    24.2    17.3  13.9 18.5                                 Tensile elongation, %                                                                       240     370     290   65   230                                  ______________________________________                                    

                  TABLE III                                                       ______________________________________                                                  Example         Control                                                       13  14     15     16   17   B   C   D                               ______________________________________                                        Polyester, parts                                                                          95    90     80   95   90   95  90  80                            Ortho ester-grafted                                                           EPDM:                                                                         Example      6     6      6   9     9   --  --  --                            Parts        5    10     20   5    10    5  10  20                            Impact strength,                                                                          64    641    849  264  844  27  32  53                            joules/m.                                                                     ______________________________________                                    

From Table II, it is apparent that the copolymer-containing compositionsof this invention have substantially higher tensile strengths andtensile elongations than the control employing an unfunctionalized EPDMcopolymer. They also have tensile strengths and elongations which arecomparable to or greater than those of the control employing an EPDMcopolymer grafted with a substantially higher proportion of glycidylmethacrylate. From Table III, it is apparent that each of thecompositions of this invention has a higher impact strength, and theproducts of Examples 14-17 a substantially higher impact strength, thanthose of the controls.

EXAMPLE 18

Following the procedure of Example 11, a similar blend was prepared inwhich the poly(butylene terephthalate) was replaced by a copolyesterprepared from 1,4-butanediol and a 0.91:1 (by weight) mixture ofdimethyl terephthalate and a dimide-diacid reaction product oftrimellitic acid and a polyoxypropylenediamine having an averagemolecular weight of about 200. Said blend had a tensile strength of 10.5MPa. and a tensile elongation of 435%. A control in which the orthoester-grafted EPDM copolymer was replaced by an EPDM copolymer graftedwith 3% glycidyl methacrylate had a tensile strength of 7.7 MPa. and atensile elongation of 505%. Again, it is apparent that ortho ester graftcopolymers may be employed at substantially lower levels offunctionalization than corresponding glycidyl methacrylate graftcopolymers, to obtain compositions of this invention having propertiesof the same order of magnitude.

What is claimed is:
 1. A copolymer-containing composition prepared bythe reaction of a polymer capable of nucleophilic substitution with apolymer comprising structural units of the formula ##STR7## wherein: R¹is C₁₋₁₀ primary or secondary alkyl or aralkyl or a C₆₋₁₀ aromaticradical or is an alkylene radical forming a second 5- or 6-membered ringwith C*, and R² is C₁₋₁₀ primary or secondary alkyl or aralkyl or aC₆₋₁₀ aromatic radical, or R¹ and R² together with the atoms connectingthem form a 5-, 6- or 7-membered ring;R³ is hydrogen or C₁₋₄ primary orsecondary alkyl; R⁴ is an unsubstituted or substituted C₁₋₆ alkylene orC₆₋₁₀ arylene radical; R⁵ is hydrogen or methyl; R⁶ is hydrogen, C₁₋₆alkyl or a C₆₋₁₀ aromatic radical; X is a substantially inert linkinggroup; m is 0 or 1; n is from 1 to 2-m; p is 0 or 1; and x is 0 when R¹and C* form a ring and is otherwise
 1. 2. A composition according toclaim 1 wherein the polymer capable of nucleophilic substitution is apolyester or polyamide.
 3. A composition according to claim 2 whereineach of R¹ and R² is alkyl and x is
 1. 4. A composition according toclaim 3 wherein m is 0 and n is
 1. 5. A composition according to claim 4wherein R³ and R⁶ are each hydrogen.
 6. A composition according to claim5 wherein p is
 1. 7. A composition according to claim 6 wherein thepolymer comprising units of formula I is a random addition polymer.
 8. Acomposition according to claim 6 wherein the polymer comprising units offormula I is a graft copolymer.
 9. A composition according to claim 8wherein the polymer comprising units of formula I is a graft copolymeron a previously formed copolymer of ethylene and propylene.
 10. Acomposition according to claim 9 wherein the polymer capable ofnucleophilic substitution is a polyester.
 11. A composition according toclaim 10 wherein R² is methyl or phenyl.
 12. A composition according toclaim 11 wherein R⁴ is methylene.
 13. A composition according to claim12 wherein the polymer comprising units of formula I is a graftcopolymer on a copolymer comprising structural units derived fromethylene, propylene and at least one non-conjugated diene.
 14. Acomposition according to claim 13 wherein the polyester is apoly(ethylene terephthalate) or poly(butylene terephthalate).
 15. Acomposition according to claim 14 wherein X is ##STR8##
 16. Acomposition according to claim 15 wherein R² is methyl.
 17. Acomposition according to claim 15 wherein R² is phenyl.
 18. Acomposition according to claim 15 wherein R⁵ is hydrogen.
 19. Acomposition according to claim 15 wherein R⁵ is methyl.
 20. Acomposition according to claim 14 wherein X is ##STR9##
 21. Acomposition according to claim 20 wherein R² is methyl.
 22. Acomposition according to claim 20 wherein R² is phenyl.
 23. Acomposition according to claim 20 wherein R⁵ is hydrogen.